Reduction of organic compounds with diborane - Chemical Reviews

Dec 1, 1976 - Clinton F. Lane. Chem. Rev. , 1976, 76 (6), pp 773–799. DOI: 10.1021/cr60304a005. Publication Date: December 1976. ACS Legacy Archive...
4 downloads 0 Views 2MB Size
Reduction of Organic Compounds with Diborane CLINTON F. LANE Aldrich-Boranes, Inc., Milwaukee, Wisconsin 53233

Received July 25, 1975 (Revised Manuscript Received October

investigation, the reaction of diborane with the carbonyl group in certain organic compounds was studied by Brown as part of his Ph.D. research.5 This is the first report on the use of B2H6 for the reduction of an organic compound. The reactions were studied on the high-vacuum line in the absence of a solvent using micro amounts of reactants. Furthermore, relatively complex equipment was required to prepare the diborane. Consequently, although the results are now considered of fundamental importance, at the time the results of this study were of negligible importance to synthetic organic chemistry. Fortunately, in 1940 a National Defense Project, initiated at the University of Chicago under the direction of Schlesinger and Brown, ultimately resulted in the development of large-scale processes for the preparation of both sodium borohydride and diborane.6 With only minor modifications these processes are now used commercially in the United States to prepare both sodium borohydride and diborane. Unfortunately, the results of these projects carried out at the University of Chicago during the war were not made public until a series of eleven articles appeared in 1953.® While preparing these articles for publication, Brown again became interested in the use of diborane as a reducing agent for organic compounds. Also, since sodium borohydride had become commercially available and provided a ready source for diborane, it was apparent that diborane should be of utility as a reducing agent for applications in synthetic organic chemistry. A preliminary communication appeared in 19579 which was followed by a full paper.10 This investigation of the reduction of organic compounds by Brown and Subba Rao was responsible for the discovery of the hydroboration reaction which kindled vigorous activity in the study of organoboranes as intermediates in organic syntheses. Both the hydroboration reaction and the chemistry of organoboranes have been reviewed by Brown and others.7·11-18 In these reviews, the use of diborane for the reduction of organic compounds is either barely mentioned or only briefly dis-

Contents Introduction

I.

The Reagent A. Preparation B. Physical and Chemical Properties C. Reaction with Acidic Hydrogens D. Borane-Lewis Base Complexes

Downloaded via EASTERN KENTUCKY UNIV on January 15, 2019 at 04:52:21 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

II.

Reductive Cleavage

III.

A. Alkenes and Alkynes B. Cyclopropanes C. Organic Halides D. Alcohols E. Ethers F.

Epoxides Miscellaneous Reduction of Organic Sulfur Compounds Reduction of Organic Nitrogen Compounds A. Imines B. Oximes C. Nitro Compounds and Related Derivatives D. Nitriles Reduction of Organic Oxygen Compounds A. Aldehydes and Ketones B. Quinones C. Carboxylic Acids D. Carboxylic Acid Anhydrides E. Esters and Lactones F. Amides Conclusions References and Notes G.

IV. V.

VI.

VII. VIII.

/.

6, 1975)

773 774 774 774 775 776 777 777 778 778 779 780 782 782 783 783 783 784 784 785 786 786 789 790 793 793 795 796 797

Introduction

Diborane, B2H6, was first isolated and characterized by Stock in 1912.1 His process involved the preparation and hydrolysis

of magnesium boride to give a mixture of higher boron hydrides. Thermal decomposition of the higher boron hydrides then gave B2H6 along with other boron hydrides. Although this pioneering work by Stock must be considered truly remarkable,2·3 the process developed by Stock was extremely tedious and gave exceedingly low yields of diborane. In 1931, Schlesinger and Burg reported an improved method for the preparation of diborane which involved passing hydrogen and boron trichloride through a silent electric discharge.4 The major product was chlorodlborane, B2H5CI, which dlsproportionated upon fractional distillation to yield diborane and boron trichloride. This procedure was satisfactory for the preparation of micro quantities of diborane, which was all that was required for the studies carried out by Schlesinger and co-workers on the Stock high-vacuum apparatus. Schlesinger and his students were attracted to the boron hydrides because their formulas, which had been established without a doubt by Stock, did not conform to the then accepted theories of valence and molecular structure. As part of their

cussed.19·20

The molecular structure, molecular properties, physical properties, and preparation of diborane are covered in a recent review.21 Also, the reaction chemistry of diborane has been reviewed with the emphasis being on the reaction of diborane with inorganic elements and inorganic compounds.22 However, a comprehensive review devoted exclusively to the selective reduction of organic compounds with diborane and related borane complexes has not appeared.23 In view of the increasing importance of selective reducing agents in synthetic organic chemistry, it was felt that such a review is both warranted and necessary. In this review the literature is covered through 1974 with several references from early in 1975. Originally, it was hoped that every reference which describes a reduction using a borane reagent could be included in this review. However, early in the literature searching it became apparent that such a comprehensive coverage would not only be extremely difficult to obtain but would also probably not be appropriate for a journal review 773

774

Clinton F. Lane

Chemical Reviews, 1976, Vol. 76, No. 6

a number of limiting factors have, by necessity, been introduced. The review deals exclusively with the use of diborane and borane-Lewis base complexes for the reduction of organic compounds. The substituted boranes, such as bis(3methyl-2-butyl)borane,25 2,3-dimethyl-2-butylborane,26 and 9-borabicyclo[3.3.1] nonane,27 which are also useful reducing agents, are not covered in this review. To be consistent and objective it was decided that a publication must meet at least one of the following criteria before it would be cited in the review: (1) the reference must illustrate the selectivity of the reagent, (2) the reference must provide some insight into the mechanism by which the reagent operates, or (3) the reference must contain a detailed experimental section. A large number of borane reductions involve the use the borane-tetrahydrofuran reagent, which will be abbreviated as BH3-THF. It should be understood that in all cases where BH3-THF is discussed, the reagent is actually a solution of the borane-tetrahydrofuran complex in tetrahydrofuran. Other abbreviations used in this article are as follows. Ac Acyl Ar Aryl BMS Borane-methyl sulfide complex Dlethylene glycol dimethyl ether Diglyme Et Ethyl Me Methyl

article. Thus,

N:

Nucleophile

Ts

Tosyl

II. The Reagent

A. Preparation Diborane, BH3-THF, BMS, and various borane-amine complexes are all available commercially. A comprehensive coverage of the preparative chemistry of diborane is included in a recent review by Long.21 Thus, only a short discussion of the more convenient methods of preparation will be given here along with some recent results. Since sodium borohydride is available commercially at a reasonable price, this chemical is the starting material of choice for the preparation of diborane. For the vacuum-line preparation of small quantities of high-purity diborane, the Schlesinger-Burg process has been replaced by several more convenient procedures. Diborane can be prepared in a vacuum line in good yield from the reaction of sodium borohydride and concentrated sulfuric acid.28 Sulfur dioxide, which is formed as a by-product, can be eliminated by the use of methanesulfonic acid in place of sulfuric acid.28 To obtain a purer sample, phosphoric acid is also recommended in place of sulfuric acid.29 A detailed literature procedure is available for the reaction of potassium borohydride with 85% orthophosphorlc acid (eq 1).30 The yield is only +



+

+

(1) 2KH2P04 40-50 %, but the purity of the diborane prepared by this method is excellent, only a trace amount of carbon dioxide ( alkenes > ketones > nitriles > epoxides > esters > acid chlorides. However, the reactivity of a given functional group can be greatly modified by the organic structure to which it is attached. It is important to recognize that these relative reactivities must be considered approximate values for simple, representative groups, and may be altered or even inverted by modifications in the molecular structure. Hopefully, the present review will help to further define the reactivity of the borane reducing agents and will assist organic chemists in deciding when it would be advantageous to utilize a borane reduction to solve a synthetic problem. It is interesting to note that the reduction of an organic compound with diborane was first disclosed at an American Chemical Society meeting in Milwaukee5 and now, 37 years later, Milwaukee is also the site of the first major effort to commercialize

Reduction of Organic Compounds with Diborane

this reaction. Finally it is ironic that the United States government spent millions of dollars on two separate research projects to develop the chemistry of sodium borohydride and diborane for unsuccessful military applications, while today the most important and successful applications for these chemicals are for the synthesis of new pharmaceuticals.

VIII.

References and Notes

(1) A. Stock and C. Massenez, Chem. Ber., 45, 3539 (1912). (2) A. Stock, “Hydrides of Boron and Silicon”, Cornell University Press, Ithaca, N.Y., 1933. (3) For brief biographies of the pioneer personalities in borane chemistry, see V. Bartow in “Borax to Boranes”, Adv. Chem. Ser., No. 32, 5-12 (4) (5)

(6) (7) (8) (9)

(10) (11) (12) (13) (14) (15) (16)

(17) (18) (19) (20) (21) (22) (23)

(24) (25)

(26) (27)

(28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38)

(39) (40)

(41) (42)

(43) (44)

(45) (46) (47) (48) (49) (50)

(1961). . I. Schlesinger and A. B. Burg, J. Am. Chem. Soc., 53, 4321 (1931). H. C. Brown, . I. Schlesinger, and A. B. Burg, J. Am. Chem. Soc., 61, 673 (1939). For a historical account of this work, see ref 7, pp 41-49. H. C. Brown, “Boranes in Organic Chemistry", Cornell University Press, Ithaca, N.Y., 1972. . I. Schlesinger and H. C. Brown in collaboration with 18 co-workers, J. Am. Chem. Soc., 75, 186-222 (1953). H. C. Brown and B. C. Subba Rao, J. Org. Chem., 22, 1135 (1957). H. C. Brown and B. C. Subba Rao, J. Am. Chem. Soc., 82, 681 (1960). H. C. Brown, “Hydroboration", W. A. Benjamin, New York, N.Y., 1962. G. M. L. Cragg, “Organoboranes in Organic Synthesis", Marcel Dekker, New York, N.Y., 1973. C. F. Lane, Aldrichimica Acta, 6, 21 (1973). H. C. Brown, Aldrichimica Acta, 7, 43 (1974). K. Smith, Chem. Soc. Rev., 3, 443 (1974). H. C. Brown, “Organic Syntheses via Boranes", with techniques by G. W. Kramer, A. B. Levy, and . M. Midland, Wiley-lnterscience, New York, N.Y., 1975. G. W. Kabalka, Aldrichimica Acta, 8, 14 (1975). T. Onak, "Organoborane Chemistry", Academic Press, New York, N.Y., 1975. Reference 7, Chapter 13. Reference 11, Chapter 17. L. H. Long, Prog. Inorg. Chem., 15, 1 (1972). L. H. Long, Adv. Inorg. Chem. Radiochem., 16, 201 (1974). The article by Brown and coworkers,24 which covers the reaction of diborane in tetrahydrofuran with various functionally substituted organic compounds, probably represents the best “review" that is currently available on this subject. H. C. Brown, P. Heim, and N. M. Yoon, J. Am. Chem. Soc., 92, 1637 (1970). H. C. Brown, D. B. Bigley, S. K. Arora, and N. M. Yoon, J. Am. Chem. Soc., 92, 7161 (1970). H. C. Brown, P. Heim, and N. M. Yoon, J. Org. Chem., 37, 2942 (1972). H. C. Brown, S. Krishnamurthy, and N. M. Yoon, J. Org. Chem., 41, 1778 (1976). H. G. Weiss and I. Shapiro, J. Am. Chem. Soc., 81, 6167 (1959). B. J. Duke, J. R. Gilbert, and I. A. Read, J. Chem. Soc., 540 (1964), A. D. Norman and W. L. Jolly, Inorg. Syn., 11, 15 (1968). G. F. Freeguard and L. H. Long, Chem. Ind. (London), 471 (1965). H. C. Brown and P. A. Tierney, J. Am. Chem. Soc., 80, 1552 (1958). G. Zwelfel and H. C. Brown, Org. React., 13, 1 (1963). H. C. Brown and R. L. Sharp, J. Am. Chem. Soc., 90, 2915 (1968). Reference 16, pp 18-21. H. C. Brown, K. J. Murray, L. J. Murray, J. A. Snover, and G. Zweifel, J. Am. Chem. Soc., 82, 4233 (1960). V. Hach, Synthesis, 340 (1974). In spite of the excess of boron hydride, complex 1 does not undergo further reduction.10 This complex (1) has been isolated from NaBH4-HOAc-THF: T. Reetz, J. Am. Chem. Soc., 82, 5039 (1960). Also, the gases evolved during the formation of 1 do not contain any diborane.39 G. W. Gribble, P. D. Lord, J. Skotnicki, S. E. Dietz, J. T. Eaton, and J. L. Johnson, J. Am. Chem. Soc., 96, 7812 (1974). The active reducing agent Is probably the complex 1 which should show some similarity to the known sodium cyanoborohydride. For a review of selective reductions using sodium cyanoborohydride, see C. F. Lane, Synthesis, 135 (1975). C. L. Yaws, J. R. Hopper, and E. M. Swinderman, Solid State Technol., 17 (11), 31 (1974). E. A. Sullivan, “Sodium Borohydride: Handling/Uses/Propertles/Analytical Procedures", Ventrón Corp., Chemicals Division, Beverly, Mass., 1973. J. S. Plzey, "Synthetic Reagents", Vol. 1, Ellis Horwood Ltd., Chichester, England, 1974, Chapter 2. This exceptionally high affinity for oxygen and, to a lesser extent, nitrogen exerts a profound influence on the chemistry of all boron compounds. For a description of this technique along with an illustration of a simple gas buret, see ref 16, pp 241-245. F. E. Martin and R. R. Jay, Anal. Chem., 34, 1007 (1962). A. B. Burg and . I. Schlesinger, J. Am. Chem. Soc., 55, 4020 (1933). W. J. Lehmann, T. P. Onak, and I. Shapiro, J. Chem. Phys., 30, 1215 (1959). W. J. Lehmann, H. G. Weiss, and I. Shapiro, J. Chem. Phys., 30, 1222 (1959). W. J. Lehmann, H. G. Weiss, and I. Shapiro, J. Chem. Phys., 30, 1226

Chemical Reviews, 1976, Vol. 76, No. 6

(51) (52) (53) (54) (55) (56) (57) (58) (59)

(60) (61) (62)

(63) (64) (65) (66)

(1959). I. Shapiro and H. G. Weiss, J. Phys. Chem., 63, 1319 (1959). W. L. Jolly and T. Schmitt, J. Am. Chem. Soc., 88, 4282 (1966). T. P. Fehlner, Inorg. Chem., 12, 98 (1973). P. A. Finn and W. L. Jolly, Chem. Commun., 1090 (1970). S. H. Rose and S. G. Shore, Inorg. Chem., 1, 744 (1962). G. E. McAchran and S. G. Shore, Inorg. Chem., 5, 2044 (1966). A. B. Burg and R. I. Wagner, J. Am. Chem. Soc., 76, 3307 (1954). E. L. Muetterties, N. E. Miller, K. J. Packer, and H. C. Miller, Inorg. Chem., 3, 870 (1964). B. M. Mikhailov, T. A. Shchegoleva, E. M. Shashkova, and V. D. Sheludyakov, Izv. Akad. Nauk SSSR, Otd. Khim. Nauk, 1218 (1962); Bull. Acad. Sci. USSR, Chem. Div., 1143 (1962). B. Z. Egan, S. G. Shore, and J. E. Bonnell, Inorg. Chem., 3, 1024 (1964). K. Niedenzu, I. A. Boenig, and E. F. Rothgery, Chem. Ber., 105, 2258 (1972). Diborane probably does not spontaneously dissociate into two borane molecules, but instead requires the influence of an appropriate electron donor reagent. C. F. Lane, Aldrichimica Acta, 6, 51 (1973). . I. Schlesinger and A. B. Burg, J. Am. Chem. Soc., 60, 290 (1938). B. Rice and H. S. Uchida, J. Phys. Chem., 59, 650 (1955). B. Rice, J. A. Livasy, and G. W. Schaeffer, J. Am. Chem. Soc., 77, 2750 (1955) J. R. Elliott, W. L. Roth, G. F. Roedel, and E. M. Boldebuck, J. Am. Chem. Soc., 74, 5211 (1952). . E. Wirth, F. E. Massoth, and D. X. Gilberg, J. Phys. Chem., 62, 870 (1958) W. D. Phillips, H. C. Miller, and E. L. Muetterties, J. Am. Chem. Soc.. 81, 4496 (1959). A. Fratiello, T. P. Onak, and R. E. Schuster, J. Am. Chem. Soc., 90, 1194 (1968). S. Yerazunls, J. W. Mullen, and B. Steginsky, J. Chem. Eng. Data, 7, 337 (1962) A. I. Gorbunov, G. S. Solov'eva, I. S. Antonov, and M. S. Kharson, Russ. J. Inorg. Chem., 10, 1074(1965). Reference 11, pp 39-44. D. F. Gaines, Inorg. Chem., 2, 523 (1963). H. C. Brown and W. J. Wallace, Abstracts of Papers, 142nd National Meeting of the American Chemical Society, Atlantic City, N.J., Sept 1962, No. N22. T. A. Shchegoleva, V. D. Sheludykov, and B. M. Mikhailov, Dokl. Akad. Nauk SSSR, 152, 888 (1963); Chem. Proc. Acad. Sci. USSR, 152, 793 (1963) This Ionic complex 14 is analogous to the well-known “diborane diammonlate". For a comprehensive review of these and related so-called "cationic boron complexes," see O. P. Shitov, S. L. Ioffe, V, A. Tartakovskii, and S. S. Novikov, Russ. Chem. Rev., 39, 905 (1970). W. A. G. Graham and F. G, A. Stone, J. Inorg. Nucí. Chem., 3, 164 (1956) T. D. Coyle, H. D. Kaesz, and F. G. A. Stone, J. Am. Chem. Soc., 81, 2989 (1959) For a recent review of the hard and soft acids and bases (HSAB) principle and the application of this concept to organic chemistry, see T.-L. Ho, Chem. Rev., 75, 1 (1975). L. M, Braun, R. A. Braun, H. R. Crissman, M. Opperman, and R. M. Adams, J. Org. Chem., 36, 2388 (1971). C. F. Lane, J. Org. Chem., 39, 1437 (1974). G. W. Kabalka and H. C. Hedgecock, Jr., J. Chem. Educ., 52, 745 (1975). C. F. Lane, Aldrichimica Acta, 8, 20 (1975). D. Ulmschnelder and J. Goubeau, Chem. Ber., 90, 2733 (1957). Reference 11, p 63. One exception has been reported where the monoalkylborane, obtained by the hydroboration of «, '-dlmethylstllbene, is cleaved under the remarkably mild conditions of dilute alkali in aqueous diglyme at room temperature.88 A. J. Weinheimer and W. E. Marsico, J. Org. Chem., 27, 1926 (1962). J. R. Johnson, H. R. Snyder, and M. G. Van Campen, Jr., J. Am. Chem. Soc., 60, 115 (1938). J. Goubeau, R. Epple, D. Ulmschnelder, and H. Lehmann, Angew. Chem., 69, 710 (1955). H. C. Brown and K. Murray, J. Am. Chem. Soc., 81, 4108 (1959). K. J. Murray, Ph.D. Thesis, Purdue University, 1961; Diss. Abstr., 22, 2993 (1962). H. C. Brown and K. J. Murray, J. Org. Chem., 26, 631 (1961). Reference 16, pp 98 and 99. H. C. Brown and G. Zwelfel. J. Am. Chem. Soc., 83, 3834 (1961). A. C. Cope, G, A. Berchtold, P. E. Peterson, and S. H. Sharman, J. Am. Chem. Soc., 82, 6370 (1960). R. Kóster, G. Bruno, and P. Binger, Justus Liebigs Ann. Chem., 644, 1 (1961). E. J. DeWitt, F. L. Ramp, and L. E. Trapasso, J. Am. Chem. Soc., 83, 4672 (1961). I. Mehrotra and D. Devaprabhakara, Tetrahedron Lett., 4871 (1972). . M. Bhagwat, I. Mehrotra, and D. Devaprabhakara, Tetrahedron Lett., 167 (1975). W. A. G. Graham and F. G. A. Stone, Chem. Ind. (London), 1096 (1957) B. Rlckborn and S. E. Wood, Chem. Ind. (London), 162 (1966). B. Rlckborn and S. E. Wood, J. Am. Chem. Soc., 93, 3940 (1971). W. J. Evers, Ph.D. Thesis, University of Maine, 1965; Diss. Abstr., 26, 4234 (1966). For a general review of the reactivity of LIAIH4, see ref 43. For a specific discussion of the reaction of LIAIH4 with organic halides, see H, C. Brown .

(67)

(68)

.

(69) (70) (71)

.

(72) (73) (74) (75)

(76)

.

(77)

(78)

.

(79)

.

(80)

(81)

(82) (83) (84) (85) (86) (87)

(88) (89) (90)

(91) (92)

(93) (94) (95) (96) (97) (98)

(99)

(100) (101)

.

(102) (103) (104) (105)

797

798

(106) (107) (108) (109) (110) (111)

(112) (113) (114) (115) (116) (117) (118)

(119) (120) (121) (122) (123) (124) (125) (126) (127) (128) (129) (130) (131) (132) (133) (134) (135) (136)

(137) (138) (139) (140)

Chemical Reviews, 1976, Vol. 76, No. 6 and S. Krishnamurthy, J. Org. Chem., 34, 3918 (1969). H. C. Brown and . M. Bell, J. Org. Chem., 27, 1928 (1962). S. Matsumura and N. Tokura, Tetrahedron Lett., 363 (1969), H. C. Brown and K. A. Keblys, J. Am. Chem. Soc., 86, 1791 (1964). D. J. Pasto and Ft. Snyder, J. Org. Chem., 31, 2773, 2777 (1966). F, G. A. Stone and W. A. G. Graham, Chem. Ind. (London), 1181 (1955). B. Bartocha, W. A. G. Graham, and F. G. A. Stone, J. Inorg. Nucí. Chem., 6, 119 (1958). M. F. Flawthorne and J. A. Dupont, J. Am. Chem. Soc., 80, 5830 (1958). R. Koster, G. Grlasnow, W. Larbig, and P. Binger, Justus Liebigs Ann. Chem., 672, 1 (1964). FI. C. Brown and S. Rhodes, J. Am. Chem. Soc., 91, 2149 (1969). P. Binger and R. Koster, Tetrahedron Lett., 156(1961). J. G. Sharefkin and S. FI. Paul. J. Org. Chem., 29, 2050 (1964). G. R. Pettit, B. Green, P. Holer, D. C. Ayres, and P. J. S. Pauwels, Proc. Chem. Soc., 357 (1962). G. P. Thakar and B. C. Subba Rao, J. Sci. ind. Res., Sect. B, 21, 583 (1962); Chem. Abstr., 59, 5117g (1963). K. M. Biswas, L. E. Houghton, and A. H. Jackson, Tetrahedron, Suppl., No. 7, 22, 261 (1966). J. Kollonitsch, J. Am. Chem. Soc., 83, 1515 (1961). H. C. Brown, U.S. Patent, 3,634,277 (1972); Chem. Abstr., 76, 74414d (1972). J. Kollonitsch, Chem. Eng. News, 52 (47), 3 (1974). D. F. Gaines, R, Schaeffer, and F. Tebbe, Inorg. Chem., 2, 526 (1963). E. Breuer, Tetrahedron Lett., 1849(1967), K. M. Biswas and A. H. Jackson, J. Chem. Soc. C, 1667 (1970), R. E. Lyle, Jr., and C. K. Spicer, Chem. Ind. (London), 739 (1963). B. Stibr, S. Hermanek, J. Plesek, and J. Stuchlik, Collect. Czech. Chem. Commun., 33, 976 (1968). D. J. Pasto, J. Am. Chem. Soc,, 84, 3777 (1962). L, H. Long and G. F. Freeguard, Nature (London), 207, 403 (1965). P. E, Sonnet, J. Heterocycl. Chem., 7, 1101 (1970). N. Janaki, K. D. Pathak, and B. C. Subba Rao, Curr. Sci., 404 (1963). B. Fleming and , I. Bolker, Can. J. Chem., 52, 888 (1974). N. Janaki, K. D. Pathak, and B. C. Subba Rao, Indian J. Chem., 3, 123 (1965) ; Chem. Abstr., 63, 5548g (1965). D. W. Theobald, J. Org. Chem., 30, 3929 (1965). K. L. Lundberg, R. J. Rowatt, and N. E. Miller, Inorg. Chem., 8, 1336 (1969). C. L. Stevens, K. J. TerBeek, and P. M. Pilla!, J. Org. Chem., 39, 3943 (1974). R. E, Lyle and D. A. Walsh, J. Organometal. Chem., 67, 363 (1974). H. Plleninger, H. Bauer, W. Bühler, J. Kurze, and U. Lerch, Justus Liebigs Ann. Chem., 680, 69 (1964). F. G. A. Stone and H. J. Emeléus, J. Chem. Soc., 2755 (1950). D. J. Pasto, C. C. Cumbo, and J. Hickman, J. Am. Chem. Soc., 88, 2201 (1966) H. C. Brown and N. M. Yoon, Chem. Commun., 1549 (1968). H. C. Brown and N. M. Yoon, J. Am. Chem. Soc., 90, 2686 (1968). J. Tanaka and A. Risch, J. Org. Chem., 35, 1015 (1970). H. Feuer and F. Brown, Jr., J. Org. Chem., 35, 1468 (1970). G. J. Beichl and J. E. Gallagher, Abstracts of Papers, 138th National Meeting of the American Chemical Society, New York, N.Y., Sept 1960, No. N112. G. H. Dorion, S. E, Polchlopek, and E. H. Sheers, Angew. Chem., Int. Ed. Engl., 3, 447 (1964). R. Molinelli, S. R. Smith, and J. Tanaka, J. Chem. Soc., Dalton Trans., 1363 (1972). M, F. Hawthorne, J. Org. Chem., 23, 1788 (1958). R. A. Baldwin and R. M. Washburn, J. Org. Chem., 26, 3549 (1961). S. Ikegami and S, Yamada, Chem. Pharm. Bull., 14, 1389 (1966); Chem. Abstr., 66, 65377k (1967). S. Yamada and S. Ikegami, Chem. Pharm. Bull., 14, 1382 (1966); Chem. Abstr., 66, 65376) (1967). J. Schmitt, J. J. Panouse, A. Hallot, H. Pluchet, P. Comoy, and P.-J. Cornu, Bull. Soc. Chim. Fr„ 816 (1963). I. Pattlson and K, Wade, J. Chem. Soc. A, 842 (1968). B. M. Mikhailov and L. S. Povarov, Zh. Obshch. Khim., 41, 1540(1971); J. Gen. Chem. USSR, 41, 1544 (1971). J. A. Blair and R. J. Gardner, J. Chem. Soc. C, 1714 (1970). J. E. McMurry, Chem. Commun., 433 (1968); J. Am. Chem. Soc., 90, 6821 (1968). J. R. Nulu and J. Nematollahi, Tetrahedron Lett., 1321 (1969). L, Caglioti and P. Grasselll, Chem. Ind. (London), 153 (1964). Sodium cyanoborohydrlde is also a useful reagent for the conversion of aldehydes and ketones to the methylene derivative via reduction of the tosylhydrazone. For a recent review of the chemistry of sodium cyanoborohydrlde, see C. F. Lane, Aldrlchimica Acta, 8, 3 (1975). L. Caglioti, Tetrahedron, 22, 487 (1966). Similar results are possible using catecholborane as the reducing agent: G. W. Kabajka and J. D. Baker, Jr., J. Org. Chem., 40, 1834 (1975). S. Cacchl, L. Caglioti, and G. Paolucci, Bull. Chem. Soc. Jpn., 47, 2323 (1974). H. Feuer and B. F. Vincent, Jr., J. Am. Chem, Soc., 84, 3771 (1962); H. Feuer, B. F. Vincent, Jr., and R. S. Bartlett, J. Org. Chem., 30, 2877 (1965). S. L. Ioffe, V. A. Tartakovskli, A. A. Medvedeva, and S. S. Novikov, /zv. Akad. Nauk SSSR, Ser. Khim., 1537 (1964); Bull. Acad. Sci. USSR, Div. Chem. Sci., 1446 (1964). H. Feuer and D. M. Braunsteln, J. Org. Chem., 34, 1817 (1969). A, Hassner and P. Catsoulacos, Chem. Commun., 590 (1967). P. Catsoulacos, J. Heterocycl. Chem., 4, 645 (1967). H. Feuer, R. S. Bartlett, B. F. Vincent, Jr., and R. S. Anderson, J. Org. .

(141) (142) (143) (144) (145)

(146) (147)

(148) (149) (150) (151) (152)

(153) (154) (155) (156)

(157) (158) (159)

(160) (161)

(162) (163) (164) (165) (166) (167) (168)

Clinton F. Lane Chem., 30, 2880 (1965).

(169) (170) (171) (172) (173)

H. Feuer and D. M. Braunstein, J. Org. Chem., 34, 2024 (1969). H. J. Emeléus and K. Wade, J. Chem. Soc., 2614 (1960). J. R. Jennings and K. Wade, J. Chem. Soc. A, 1946 (1968).

J. Tanaka and J. C. Carter, Tetrahedron Lett., 329 (1965). S. Bresadola, F. Rossetto, and G. Puosl, Tetrahedron Lett., 4775

(1965). R. O. Hutchins and B. E. Maryanoff, Org. Syn., 53, 21 (1973). A. J. Leffler, Inorg. Chem., 3, 145 (1964). B. C. Subba Rao and G. P. Thakar, Cur. Sci., 404 (1963). J. S. Fowler, R. R. MacGregor, A. N. Ansari, H. L. Atkins, and A. P. Wolf, J. Med. Chem., 17, 246 (1974). (178) M. W. Rathke and H. C. Brown, J. Am. Chem. Soc., 88, 2606 (1966). (179) T. P. Fehlner, Inorg. Chem., 11, 252 (1972). (180) L. P. Kuhn and J, O. Doali, J. Am. Chem. Soc., 92, 5475 (1970). (181) S. L. Ioffe, V. A. Tartakovskli, and S. S. Novikov, Izv. Akad. Nauk SSSR, Ser. Khim., 622 (1964); Bull. Acad. Sci. USSR, Div. Chem. Sci., 582 (1964). (182) A. Pelter and T. E. Levitt, Tetrahedron, 26, 1545 (1970). (183) H. Noth and L. P. Winter, Angew. Chem., 71, 651 (1959). (184) H. C. Brown and V. Varma, J. Am. Chem. Soc., 88, 2871 (1966). (185) H. C. Brown and D. B. Blgley, J. Am. Chem. Soc., 83, 3166 (1961). (186) M. G. Combe and . B. Hen best, Tetrahedron Lett., 404 (1961). (187) J. Klein and E. Dunkelblum, Tetrahedron, 23, 205 (1967). (188) J. Klein and E. Dunkelblum, Isr. J. Chem., 5, 181 (1967). (189) W. M. Jones, J. Am. Chem. Soc., 82, 2528 (1960). (190) Y. Bessiere-Chretien, G. Boussac, and M. Barthelemy, Bull. Soc. Chim. Fr„ 1419 (1972). (191) The reduction of 2-alkylcycloalkanones with lithium or potassium trisec-butylborohydride gives pure c/s-2-alkylcycloalkanols; H. C. Brown and S. Krishnamurthy, J. Am. Chem. Soc., 94, 7159 (1972); C. A. Brown, ibid., 95, 4100 (1973). (192) The hydroboration-oxldatlon of 1-alkylcycloalkenes gives pure trans2-alkylcycloalkanols: H. C. Brown and G. Zweifel, J. Am. Chem. Soc., 83, 2544 (1961). (193) The reduction of ,/3-unsaturated aldehydes and ketones with 9-borablcyclo[3.3.1]nonane (9-BBN) provides a convenient and selective procedure for the preparation of allylic alcohols: S. Krishnamurthy and H. C. Brown, J. Org. Chem., 40, 1864 (1975). (194) M. Stefanovic and S. Lajslc, Tetrahedron Lett., 1777 (1967). (195) J. Klein and E. Dunkelblum, Tetrahedron, 24, 5701 (1968). (196) P. L. Southwick, N. Latif, B. M. Fitzgerald, and N. M. Zaczek, J. Org. Chem., 31, 1 (1966). (197) E. Dunkelblum, R. Levene, and J. Klein, Tetrahedron, 28, 1009 (1972). (198) J. I. Seeman and H. Ziffer, J. Org. Chem., 39, 2444 (1974), (199) Y. Chretien-Bessiere, Bull. Soc. Chim. Fr„ 2182 (1964). (200) I. Mldgley and C. Djerassi, Tetrahedron Lett., 4673 (1972). (201) L. Caglioti, G. Cainelli, G. Maina, and A. Selva, Gazz. Chim. /fa/., 92, 309 (1962); Chem. Abstr., 57, 12572c (1962). (202) L. Caglioti, G. Cainelli, G. Maina, and A. Selva, Tetrahedron, 20, 957 (1964). (203) L. Caglioti, G. Cainelli, and A. Selva, Chim. Ind. (Milan), 44, 36 (1962); Chem. Abstr., 60, 12075d (1964). (204) J. Klein, E. Dunkelblum, and D. Avrahami, J. Org. Chem., 32, 935 (1967) (205) G. R. Pettit, B. Green, G. L. Dunn, P. Hofer, and W. J. Evers, Can. J. Chem., 44, 1283 (1966). (206) R. L. Clarke, A. J. Gambino, and S. J. Daum, J. Med. Chem., 17, 1040 (1974); S. J. Daum, A. J. Gambino, and R. L. Clarke, J. Org. Chem., 39, 2566 (1974). (207) . B. Bhat and K. Venkataraman, Tetrahedron, 19, 77 (1963). (208) W. J. Wechter, J. Org. Chem., 28, 2935 (1963). (209) J. A. Ballantine, A. H. Jackson, G. W. Kenner, and G. McGilllvray, Tetrahedron, Suppl., No. 7, 22, 241 (1966). (210) K. M. Biswas and A. H. Jackson, Tetrahedron, 24, 1145(1968). A. H. Jackson, B. Naldoo, and P. Smith, Tetrahedron, 24, 6119 (1968). (211) (212) E. Dunkelblum, Tetrahedron, 28, 3879 (1972). (213) W. A. Remers, R. H. Roth, and M. J. Weiss, J. Am. Chem. Soc., 86, 4612 (1964). (214) C. Temple, Jr,, J. D. Rose, and J. A. Montgomery, J. Med. Chem., 17, 615 (1974) (215) D. S. Bapat, B. C. Subba Rao, . K. Unni, and K. Venkataraman, Tetrahedron Lett., No. 5, 15 (I960). (216) N. M. Yoon, C. S. Pak, H. C. Brown, S. Krishnamurthy, and T. P. Stocky, J. Org. Chem., 38, 2786 (1973). (217) C. F. Lane, H. L. Myatt, J. Daniels, and . B. Hopps, J. Org. Chem., 39, 3052 (1974). (218) C. F. Lane, Aldrichimica Acta, 7, 7 (1974). (219) M.-L. Anhoury, M. Arickx, P. Crooy, R. DeNeys, and J. Eliaers, J. Chem. Soc., Perkin Trans. 1, 191 (1974). (220) N. J. McCorkindale, T. P. Roy, and S. A. Hutchinson, Tetrahedron, 28, 1107 (1972). (221) S. Hagishita and K. Kuriyama, Tetrahedron, 28, 1435 (1972). (222) H. Kluender, F.-C. Huang, A, Fritzberg, H. Schnoes, C. J. Sih, P. Fawcett, and E. P. Abraham, J. Am. Chem. Soc., 96, 4054 (1974). (223) N. L. Alllnger and L. A. Tushaus, J. Org. Chem., 30, 1945 (1965). C. C, Shroff, W. S. Stewart, S, J. Uhm, and J, W. Wheeler, J. Org. Chem., (224) 38, 3356(1971). (225) W. Herz, M. Gopal Nair, and D. Prakash, J. Org. Chem., 40, 1017 (1975) (226) E. J. Corey and H. S. Sachdev, J. Org. Chem., 40, 579 (1975). (227) O. Yonemltsu, Y. Hamada, and Y. Kanaoka, Tetrahedron Lett., 3575 (1968) (228) C.-K. Wat, V. S. Malik, and L. C. Vlnlng, Can. J. Chem., 49, 3653 (1971). (229) F. J. McEvoy and G. R. Allen, Jr., J. Org. Chem., 38, 3350 (1973).

(174) (175) (176) (177)

.

.

.

.

Reduction of Organic Compounds with Diborane (230) A. H. Jackson and B, Naidoo, Tetrahedron, 25, 4843 (1969). (231) R. Iyer, A. H. Jackson, P. V. R. Shannon, and B. Naidoo, J. Chem. Soc., Perkin Trans. 2, 872 (1973). (232) F. Smith and A. M. Stephen, Tetrahedron Lett., No. 7, 17 (1960). (233) E. L. Hirst, E. Percival, and J. K. Wold, J. Chem. Soc., 1493 (1964). (234) J. H. Manning and J. W. Green, J. Chem. Soc. C, 2357 (1967). (235) A. F. Rosenthal and . Z. Atassi, Biochim. Biophys. Acta, 147, 410 (1967). (236) . Z. Atassi and A. F. Rosenthal, Biochem. J., 111, 593 (1969). O. Yonemitsu, Y. Hamada, and Y. Kanaoka, Chem. Pharm. Bull., 17, 2075 (237) (1969). (238) J. K. Hecht and C. S. Marvel, J. Polymer Sci., Part A-1, 5, 685 (1967). (239) D. G. M. Diaper and W. M. J. Strachan, Can. J. Chem., 45, 33 (1967). (240) R. Littell and G. R. Allen, Jr., J. Org. Chem., 38, 1504 (1973). (241) J. Plesek, S. Hermanek, and A. Petrina, Czech Patent 149,279 (1973); Chem. Abstr., 79, 146061y (1973). (242) B. C. Subba Rao and G. P. Thakar, Curr. Sci., 29, 389 (1960). R. A, Firestone, E. E. Harris, and W. Reuter, Tetrahedron, 23, 943 (243) (1967). (244) K. M. Biswas and A. H. Jackson, Tetrahedron, 25, 227 (1969). (245) M. Chaykovsky and A. Rosowsky, J. Org. Chem., 36, 3067 (1971). (246) L. J. Dolby and Z. Esfandlari, J. Org. Chem., 37, 43 (1972). (247) A. Pelter, M. G. Hutchings, T. E. Levitt, and K. Smith, Chem. Commun., 347 (1970). (248) J. Cason, D. M. Lynch, and A. Weiss, J. Org. Chem., 38, 1944 (1973). J. Cason, A. Weiss, and S. A. Monti, J. Org. Chem., 33, 3404 (1968). (249) (250) R. E. White and Z. G. Gardlund, J. Polym. Sci., Part A-1, 8, 1419 (1972) (251) Ester groups can be selectively reduced with BH3-THF in the presence of carbonate linkages under conditions whereby LiAIH4 not only reduces the ester, but also severely degrades the polycarbonate.250 (252) A. H. Jackson, G. W. Kenner, and G. S. Sach, J. Chem. Soc. C, 2045 (1967). (253) A. H. Jackson and B. Naidoo, J. Chem. Soc., Perkin Trans. 2, 548 (1973) (254) P. E. Sonnet, J. Heterocycl. Chem., 9, 1395 (1972). (255) W. C. Still, Jr. and D. J. Goldsmith, J. Org. Chem., 35, 2282 (1970). (256) J. W. Clark-Lewis and E. J, McGarry, Aust. J. Chem., 26, 819 (1973). (257) G. P. Thakar, N. Janaki, and B. C. Subba Rao, Indian J. Chem., 3, 74(1965); Chem. Abstr., 63, 571f (1965). (258) B. S. Kirklacharian, Chem. Commun., 162 (1975). a leading reference which also contains an interesting mechanistic For (259) discussion, see J. R. Dias and G. R. Pettit, J. Org. Chem., 36, 3485 (1971). (260) G. R. Pettit, U. R. Ghatak, B. Green, T. R, Kasturi, and D, M. Piatak, J. Org. Chem., 26, 1685 (1961), (261) G. R. Pettit and D. M. Piatak, J. Org. Chem., 27, 2127 (1962). (262) G. R. Pettit and W. J. Evers, Can. J. Chem., 44, 1293 (1966). (263) G. R. Pettit and W. J. Evers, Can. J. Chem., 44, 1097 (1966). (264) G. R. Pettit and T. R. Kasturi, J. Org. Chem., 26, 4557 (1961). (265) G. R. Pettit, J. C. Knight, and W. J. Evers, Can. J. Chem., 44, 807 (1966). (266) A. Marxer, H. R. Rodriguez, J. M. McKenna, and . M. Tsai, J. Org. Chem., 40, 1427 (1975). (267) G. R. Pettit, T. R. Kasturi, B. Green, and J. C. Knight, J. Org. Chem., 26, 4773 (1961). (268) G. R. Pettit and J. R. Dias, Chem. Commun., 901 (1970). (269) H. C. Brown and P. Heim, J. Am. Chem. Soc., 86, 3566 (1964). (270) H. C. Brown and P. Heim, J. Org. Chem., 38, 912 (1973). .

.

Chemical Reviews, 1976, Vol. 76, No. 6

799

(271) R. Kuttan, A. N. Radhakrishnan, T. Spande, and B. Witkop, Biochemistry, 10, 361 (1971). (272) D. L. Coffen, D. A. Katonak, and F. Wong, J. Am. Chem. Soc., 96, 3966 (1974) (273) J. W. Daly, J. Benigni, R. Minnis, Y. Kanaoka, and B. Witkop, Biochemistry, 4, 2513 (1965). (274) W. F. Gannon, J. D. Benigni, J. Suzuki, and J. W. Daly, Tetrahedron Lett., 1531 (1967). (275) J. I. DeGraw and W. A. Skinner, Can. J. Chem., 45, 63 (1967). K. Wiesner, Z. Valenta, D. E. Orr, V. Liede, and G. Kohan, Can. J. Chem., (276) 46, 3617 (1968). (277) M. Julia, F. LeGoffic, J, Igolen, and M. Baillarge, Tetrahedron Lett., 1569 (1969) (278) D. L. Trepanier and S. Sunder, J. Med. Chem., 16, 342 (1973). (279) Z. B. Papanastassiou and R. J. Bruni, J. Org. Chem., 29, 2870 (1964). (280) G. R. Pettit, S. K. Gupta, and P. A. Whitehouse, J. Med. Chem., 10, 692 (1967) (281) R. D. Schuetz, G. P. Nilles, and R. L. Titus, J. Org. Chem., 33, 1556 (1968) (282) P. L. Warner, Jr., and T. J. Bardos, J. Med. Chem., 13, 407 (1970). (283) J. B. Hester, Jr., A. D. Rudzik, and W. Veldkamp, J. Med. Chem., 13, 827 (1970) (284) K. Ishlzumi, S. Inaba, and H. Yamamoto, J. Org. Chem., 37, 4111 (1972) (285) D. L. Coffen, R. I. Fryer, D. A, Katonak, and F. Wong, J. Org. Chem., 40, 894 (1975). (286) P, S. Portoghese and J. G. Turcotte, J. Med. Chem., 14, 288 (1971). (287) W. B. Wright, Jr., U.S. Patent 3,565,902 (1971); Chem. Abstr., 75, 36033a (1971) (288) W. T. Colwell, G. Chan, V. H. Brown, J. I. DeGraw, and J. H. Peters, J. Med. Chem., 17, 142 (1974). (289) N. B. Chapman, R. M. Scrowston, and R. Westwood, J. Chem. Soc. C, 528 (1967). (290) J. C. Hinshaw, J. Org. Chem., 40, 47(1975). (291) H. J. Brabander and W. B. Wright, Jr., J. Org. Chem., 32, 4053 (1967). (292) R. Littell and G. R. Allen, Jr., J. Org. Chem., 33, 2064 (1968). (293) N. W. Gilman and L. H. Sternbach, Chem. Commun., 465 (1971), (294) H. Zinnes, R. A. Comes, and J. Shavel, Jr., J. Heterocycl. Chem., 5, 875 (1968). (295) A. F. McKay and G. R. Vavasour, Can. J. Chem., 32, 639 (1954). (296) E. R. Bissell and M. Finger, J. Org. Chem., 24, 1256 (1959). (297) A. Kalir, Z. Pelah, and D. Balderman, Isr. J. Chem., 5, 101 (1967); Y. Kobayashi, I. Kumadaki, Y. Hírose, and Y. Hanzawa, J. Org. Chem., 39, 1836 (1974). (298) R. A. Johnson, H. C. Murray, L. M. Reineke, and G. S. Fonken, J. Org. Chem., 33, 3207 (1968). (299) . P. Mertes and A. J. Lin, J. Med. Chem., 13, 77 (1970). (300) R. J. Schultz, W. H. Staas, and L. A. Spurlock, J. Org. Chem., 38, 3091 (1973) ; W. H. Staas and L. A. Spurlock, ibid., 39, 3822 (1974). (301) A. Chatterjee and K. M. Biswas, J. Org. Chem., 40, 1257 (1975). W. V. Curran and R. B. Angier, J. Org. Chem., 31, 3867 (1966). (302) (303) M. J, Kornet, P. A. Thio, and S. I. Tan, J. Org. Chem., 33, 3637 (1968). (304) H. Sirowej, S. A. Khan, and H. Plieninger, Synthesis, 84 (1972). (305) B. Dietrich, J. M. Lehn, J. P. Sauvage, and J. Blanzat, Tetrahedron, 29, 1629 (1973); B. Dietrich, J. M. Lehn, and J. P. Sauvage, ibid., 29, 1647 (1973). (306) P. Attanasi, L. Caglioti, F. Gasparrlni, and D. Misiti, Tetrahedron, 31, 341 (1975) (307) H. C. Brown and W. Korytnyk, J. Am. Chem. Soc., 82, 3866 (1960). .

.

.

.

.

.

.

.